Thermoplastic protein composition



Patented M 8; e e I a v ,202,623

UNITED STATES PATENT OFFICE THERMOPLASTIC PROTEIN COMPOSITION Jean Delorrne, Aubiere, France, aasignor to George Mon-ell Corporation, Muske gon,-Mich.,

a corporation of Michigan:

No Drawing. Application December 30, 1937, Serial No. 182,473

3 Claims. (Cl. 260-119) This invention is for the production of thermoa temperature of ordinary atmospheric or room plastic compositions produced byvthe treatment temperature. The= time of approximately of proteins, and particularly casein, which is a hours is subject to variation and 'rnay bad practical protein and which I have treated in creased with the use 'of higher temperatures the hereafter described manners. though the emper re h uld not be raised 6 Fundamentally the treatment consists in subabove approxi y 65 01' 70 C; The time of j'ecting the chosen protein, such as casein, to the .15 hours is 'the best time which I have fo nd action of a halide or sulphate of the aliphatic for the mixture to stand with ordinary m i alcohols as methyl, ethyl, propyl, butyl, etc.. In t ns f atm sp temperatur and humidity.

practice the treatment is in connection with and After the intermixed ingredients above speci- 10 i th presence of glkalls, uch a au ti soda. fied have stood for approximately the time stated, or t or th carbonates of di potasthere is added 5 kilograms of ethyl sulphate, for sium or ammonium, or in materials I carrying example, gradually stirring it into the mass and such ingredients, for example, lime, barytes, calafter thoroughly irl rm ewi h then I cium carbonate, barium carbonate and the like. e t g at a temperature ranging between 80 1 When the casein or other equivalent protein to 30. for a pe of from 3 to 5 hours. The has been t t and t d upon by a'haud reaction is complete upon the attainment of a or sulphate of the aliphatic alcohols and the Smooth clear liquid which is e t yf a y resulting product of the reactions washed and Solid P c es. nodules maSSeS- It y otherwise purified of any excess of materials the! be noted that instead of first mixing the 20 greater t is requiredio complete th casein, the alkali carbonate and the alcohol as tion and thereafter dried, there is produced a Stated and, after a period of time, introducing. product or composition which is solid at ordithe ethyl p ate and the heating a d m nary atmospheric temperatures, which becomes 1 four ingredients y be initially mixed tosoft at approximately 110 C. and is sufficiently erend le to S d fo the period of time, 25

plastic for forming 'or rolling at approximately h which e e ti g o the higher pe a- 80 C., which may be and preferably is ground ture with the simultaneous continuous mixing into a finely divided form foruse in injection W be performed. molding or for molding into mold cavities under Under these conditions at e e ing of the t d pressure, whi is readily d d to reaction the mass of ingredients is slightly aura-"80 an easily workable plastic form by the treatment e in character b t the alkalinity is weak and thereof with numerous so-called plastiflers and not Sufilelently asic to ca y y y is of which in plastic form may be rolled and extended e ein protein At the end of the reaction into sheets of any desired thinness which sheets the cfimpesitien m y be substantially utral- 0!" after rolling are flexible at ordinary temperas ightly aeidifi After the reaction 18 0011191815835 tures. The composition produced may be used the product b d y e c o ed and freed in various types and characters to increase the of any excess of ethyl u p by washing with bulk, to modify and change the physical appeara solvent thereof such as alcohol, the usual fllance and characteristics from the unadulterated termg decanting methods being used to ther 40 product of this invention. The product obtained remove e l, the product then dried. Q in eflect is similar in many respects to Celluloid such Product is of gelatinous character, is solid and may be availed of in the production of a largeand may be of a granular 101m at ph ric quantity of articles analogous to those obtained temperatures and can e ground into a desired with oellulosic ethers and esters and the like. finely or coarsely divided form a m y be pre- 48 This invention has been reduced to practice Such final Product Obtained as described 4! by using casein. A practical and concrete is readily usable in substantially the samemam. ample, of the process which I employ and which many other Plastic t a u hs has produced the most s'ati factor 're lt is to Cel1ulold and various thermoplastic mcldingpow. -provide and mix in a containing vessel, 10 kilo- (161's and is available use in the same inan- 50 grams of sulphuric casein; 3.5 kilograms of an- A5 a thermeplastie melding Powder itxmayy hydrous sodium carbonate in powdered form; and' be used melding by mpr sion or injection.

.10 liters of denatured alcohol to These AS a Celluloid Substitute it may be used for the ingredients are thoroughly and homogeneously fabrication of films, caps or closures'for recep-- mixed and then left to stand to act upon each tacles, as theintermediate layer in safety glass, Ii other for a period of approximately 15 hours at and many other purposes. It is soluble ina great '55 alcoholic sulphates stated upon the casein to many solvents among which are chlorinated solvents, carbon sulphide, alcohol, cyclohexanol, methylglycol dioxane, esters and ethers, benzald hyde, furfurol, acrolein, aniline, acetone, methy thyl acetone, mesityl oxide, pyridine,.as well a in the formic, acetic, butyric, stearic, oleic va ids etc. It is capable of being softened or plastified by a great many compositions for such purpose, including glycerol, bornylacetate, triacetine, ethyl ricinoleate, diethyl phthalate, di-

butyl phthalate, ethyl lactate, butyl lactate, tri-' aryl phosphate, acetophenone, fenchone, cam-v wood extracts, etc. By itself it is clear and transparent and does not deteriorate or change under the action of water and light.

The above example is for the best process for the production of the product that'I have so far discovered. The change in the casein or similar protein to the desired product may be performed specifically in a different manner. As an example in a mixer 8 kilograms of rennet-casein, 6 kilograms of denatured alcohol at 90, and 3.2 kilograms of ethyl sulphate are thoroughly mixed and heated from 4 to 8 hours-at a temperature approximating 80 C., the heating continuing until a completely smooth, viscous fluid is obtained without any solid materials therein, this evidencing that the reaction is complete. The mixer and its contents may then be cooled and 10 liters of cold water added to effectuate and help precipitation of the gelatinous thermoplastic product which is obtained. In this case the reaction begins in a neutral medium but there is a production of some acid, such as H2804, during the reaction and the acidity is sufficient when approachi-ng' the end of the reaction that there are produced violet or brown colorations due to the partial hydrolysis of the protein because of the acid condition. The product therefore is not as satisfactory as in the first described ex ample, but this second example is indicative of the reaction effect of ethyl sulphate or the other produce the thermoplastic composition desired.

In the presence of a tanning or hardening agent-like formaldehyde, or in using other proteins which have been hardened, for a part or all of the casein or equivalent protein content in the above example, more difiiculty is encoun- -'tered in obtaining the desired products, it appearing that the amine functions, -NH2, are

net-casein mixed with 2.5'kilograms of caustic liters of water.

soda which has been dissolved in from 15 to 25 The mixing is continued until there is a completely homogeneous mass obtained. Thereupon 5 kilograms of ethyl sulphate are added by stirring the same in slowly. The complete mixture is to be heated to a temperature of about 65 C. and at the same time mixed and agitated. The reaction which takes place is of an exothermic character so that the temperature soon reaches C. at which point it should be approximately held. The heating and agitating for a completion of the reaction takes from 3 to 5 hours. The contents produced is colorless and viscous, fairly well soluble in water an forms a gelatine with aqueous alcohols.

The same process immediately above appearingv may be followed in the presence of formaldehyde in the proportion of 50 parts of the formaldehyde at 30% strength to 100 partsof casein. Likewise casein or other proteins may be used which have been subjected to a tanning or hardening operation.- But in such case the reaction is less pronounced in violence, the product obtained is less viscous and less soluble in water and in the various organic solvents.

The ways disclosed of treating the casein or other protein with an alcoholic sulphate or halide produce a solid thermoplastic composition at ordinary atmospheric temperatures and, particularly in the first example given, it is clear, transparcnt and without discolorations. But in all cases the products obtainedare thermoplastic and may be pressed under hydraulic pressure into molds and subjected to the application of heat and be very useful as a thermoplastic powder in injection molding, for best results using a softening agent or plastifier. The discolorations produced in the product in the second example given are objectionable for some purposes but are not .bonate, an ethyl alcohol of approximately 80 to purity, the remainder being principally water, and ethyl sulphate, ageing said mixture at ordinary atmospheric or room temperatures and 45 then stirring and heating said intermixed ingredients and maintaining the same at a temperature of approximately 80 to 85 C. and maintaining said mixing and temperatures until reactions are complete, evidenced by the production of a smooth, homogeneous liquid free of solid particles or masses.

2. The herein described process which consists, in intermixing an acid casein, an unhydrated alkali carbonate, ordinary denatured ethyl alcohol and ethyl sulphate in the approximate proportions of 20 parts by weight of casein, 7 parts by weight of the alkali carbonate, 18 parts by weight of alcohol and '10 parts by weight of ethyl sulphate, ageing said mixture for a period of approximately 15 hours at ordinary atmospheric temperatures and thenv stirring and heating said intermixed. ingredients to a temperature approximately 80 to 85 C. and maintain-. ing the mixing and temperature for a period of approximately 3 to 5 hours or until reactions are complete.

' 3. A thermoplastic composition of matter provided by the reaction upon sulphuriccasein of ethyl sulphate in the presence of ethyl alcohol and a relatively weak alkali salt, the acid radical of which is weaker than the acid radical'of the casein.

JEAN osmium. 9 

